Lecture 11

CHEMISTRY (CY11003)
Spring 2020 -2021

LECTURE –11
(28th December)
Department of Chemistry,
Indian Institute of Technology Kharagpur
Chemical Equilibrium:
Reactions in Gas Phase: Ideal Gases:
A(g) ⇋ B(g)
Let the reaction advance by = ξ moles
The change in No. mole of A, dnA = − dξ
The change in No. mole of B, dnB = + dξ
At constant T and P, dG = μA dnA + μB dnB
dG = ‒ μA dξ + μB dξ dG = (μB ‒ μA ) dξ
(∂G /∂ ξ)T, P = (μB ‒ μA )
(∂G /∂ ξ)T, P < 0, forward reaction => μA > μB

(∂G /∂ ξ)T, P > 0, reverse reaction => μB > μA
For the reaction, ν1 X1 + ν2 X2 + ν3 X3 + … ⇋ νn-1 Xn-1 + νn-2Xn-2 + νn-3 Xn-3 + …
or, 0 = ∑νi Xi
ni = nio + νi dξ or d(ni ‒ nio ) = νi dξ
=> dni = νi dξ
dG = ∑ μi dni dG = (∑ νi μi )dξ
(∂G /∂ ξ)T, P = ΔrG ΔrG = ∑νi μi

ΔrG < 0 forward reaction is spontaneous (∂G /∂ ξ)T, P < 0
ΔrG > 0 reverse reaction is spontaneous (∂G /∂ ξ)T, P > 0
ΔrG = (∑νi μi )eq= 0 reaction is at equilibrium (∂G /∂ ξ)T, P,eq = 0

ξ has a limited range of variation between a least value, ξl and a
greatest value , ξg
At any composition of the mixture, G = ∑ni μi
G = ∑ni (μi o + μi − μi o ) = ∑ni μi o(T, P) + ∑ni (μi − μi o )
Gpure = ∑ni μi o(T, P)
ΔGmix = ∑ni (μi − μi o )

G = Gpure + ΔGmix
(∂G /∂ξ)T, P = (∂Gpure /∂ξ)T, P +
(∂ΔGmix /∂ξ)T, P
At equilibrium,
(∂Gpure /∂ξ)eq = − (∂ΔGmix /∂ξ)eq

Chemical Equilibrium: Reactions in Gas Phase
aA(g) ⇋ bB(g) or 0 ═ bB(g) ‒ aA(g)
ΔrG = ∑νi μi => ΔrG = bμB ‒ aμA
For ideal gases, μi = μio + RT ln Pi /Po where Po = 1 bar
μA = μAo + RT ln PA /Po μB = μBo + RT ln PB /Po

ΔrG = bμBo + bRT ln(PB /Po) ‒ aμAo ‒ aRT ln(PA /Po)
ΔrG = (bμBo ‒ aμAo) + bRT ln(PB /Po) ‒ aRT ln(PA /Po)
ΔrG = ΔrGo + RT ln[(PB /Po)b /(PA /Po)a ] ΔrG = ΔrGo + RT lnQ

ΔrGo = (bμBo ‒ aμAo) Q = [(PB /Po)b /(PA /Po)a ] Q = ∏ Piνi (Po)−∆ν
At equilibrium, ΔrG = 0 ΔrGo = ‒ RT ln[(PB /Po)b /(PA /Po)a ]eq
ΔrGo = ∑νi μio ΔrGo = ‒ RT ln Kp Kp = [(PB /Po)b /(PA /Po)a ]eq

Chemical Equilibrium: Reactions in Gas Phase
• ΔrGo is a function of T and depends on
ΔrGo = ‒ RT lnKP the nature of reactants and products;
• ΔrGo is generally not equal to zero;
KP = [(PB /Po)b /(PA /Po)a ]eq
= [(PB)b /(PA)a ]eq (Po)a-b When ΔrGo = 0, KP = 1
KP = ∏Piνi (Po)−∆ν
• KP is thermodynamic
equilibrium constant;
• KP is dimensionless;
• At constant T, KP does not
depend on pressure;
• KP depends on temperature
only;
∆ν = ∑ν (products) − ∑ν (reactants)
Equilibrium Constants: Ideal Gases
KP = ∏ (Pi)eνi (Po)−∆ν xi = Pi /P or Pi = xi P
KP = ∏ xiνi P∆ν (Po)−∆ν KP = Kx (P/Po)∆ν
Kx = ∏ xiνi
Pi = ni RT/V; ci = ni /V or Pi = ci RT;
Pi = ci (co RT/ Po) KP = ∏ (ci)eνi (co RT/ Po)∆ν

where co = 1 mol L−1 ; ci = ci /(1 mol L−1)
KP = Kc (co RT/ Po)∆ν Kc = ∏ ciνi

Chemical Equilibrium: Real Gases
Real Gases: μi = μio + RT ln fi /Po Lim f = P
P→0
f is fugacity γ = f /P f = γP
Lim γ = 1
For the reaction, aA(g) ═ bB(g) P→0
ΔrGo = ‒ RT lnKf
Kf = (fB /Po)b /(fA /Po)a
= (fB)b /(fA)a (Po)a-b
= (γB PB)b /(γA PB)a (Po)a-b
= (γB)b /(γA)a x (PB)b /(PA)a (Po)a-b
Kf = Kγ KP Kγ = (γB)b /(γA)a
Kf is thermodynamic eqm. constant
KP is apparent eqm. constant, and a dimensionless quantity
Chemical Equilibrium: Reactions in Solution
For the reaction, aA ⇋ bB where A and B are
nonelectrolyte solutes
Assuming ideal behavior, μA = μAo + RT ln (mA /mo)
ΔrGo = ‒ RT lnKm μB = μBo + RT ln (mB /mo)
Km = (mB /mo)b /(mA /mo)a For nonequilibrium reactions,

ΔrG = ΔrGo + RT lnQ
Km = (mB)b /(mA)a (mo)a-b
Q is reaction quotient
Kc = ([B] /co)b /([A] /co)a Q = ∏ Piνi (Po)−∆ν
Kc = [B]b /[A]a (co)a-b Q = ∏ fiνi (Po)−∆ν
mo = 1 mol kg−1 = 1 m co = 1 mol L−1 = 1 M Q = ∏ miνi (mo)−∆ν

Chemical Equilibrium: Reactions in Solution
For nonideal solutions, μi = μio + RT ln ai ΔrGo = ‒ RT lnKa
The thermodynamic Lim a = m
equilibrium constant, Ka = (aB)b /(aA)a m→0
Lim γm = 1
m→0
Ka = (γB)b /(γA)a x (mB /mo)b /(mA /mo)a
Lim a = c
Ka = Kγ Km Where Kγ = (γB)b /(γA)a c→0
Lim γc = 1
c→0
Lim a = x
x→0
Lim γx = 1
x→0
Chemical Equilibrium: Heterogeneous Equilibria
CaCO3 (s) ⇋ CaO (s) + CO2 (g)
K΄c = [CaO] [CO2] /[CaCO3]
K΄c × [CaCO3] /[CaO] = [CO2] Kc = [CO2]
KP = PCO2 / 1 bar Ka = aCaO aCO2 /aCaCO3
Ka = fCO2 / 1 bar aCaO = 1 and aCaCO3 = 1
Ka = aCO2
Equilibrium Constant: Effect of Temperature
ΔrGo/ T = ‒ R lnK [∂(ΔrGo/ T)/∂T]P = ‒ (ΔrHo/ T2 )
[∂(‒R lnK)/∂T]P = ‒ (ΔrHo/T2) [∂lnK/∂T]P = ΔrHo/(RT2 )
If ΔrHo is independent of temperature, i.e. ΔCp = 0
ln(K2/K1) = ΔrHo/ R (T2 − T1)/ (T2T1)

van’t Hoff equation
‒ ΔrGo/R T = lnK
ΔrGo = ΔrHo ‒ T ΔrSo
lnK = ‒ ΔrHo/RT +ΔrSo /R

Equilibrium Constant: Effect of Temperature
If ΔrHo is NOT independent of temperature, i.e. ΔCp ≠ 0
ΔrHo(T) = ΔrHo(298) + ∫T ΔCp dT => ΔrHo(T) = ΔrHo(298) + ΔCp (T – 298)
ΔrSo(T) = ΔrSo(298) + ∫T (ΔCp/T) dT => ΔrSo(T) = ΔrSo(298) + ΔCp ln(T/298)
ΔrGo(T) = ΔrHo(T) – T ΔrSo(T) =>
ΔrGo(T) = ΔrHo(298) + ΔCp(T – 298) – T [ΔrSo(298) + ΔCp ln(T/298)]
ΔrGo(T) = ΔrHo(298) – T ΔrSo(298) + ΔCp (T – 298) – T ΔCp ln(T/298)

lnKT = – ΔrHo(298)/RT + ΔrSo(298)/R – ΔCp (T – 298)/RT + ΔCp ln(T/298)/R
RTlnKT = RTlnK298 – ΔCp (T – 298) + T ΔCp ln(T/298)
lnKT – lnK298 = – ΔCp(T – 298)/RT + ΔCp ln(T/298)/R

ln(KT/K298) = – ΔCp(T – 298)/RT + ΔCp ln(T/298)/R
Equilibrium Constant: Effect of Pressure
ΔrGo does NOT vary with the change in
ΔrGo = ‒ RT lnKP pressure, (∂KP/∂P)T = 0
KP is independent of P if the reaction involves ideal gases
KP does depend on P if the reaction involves real gases
For reactions involving ideal gases, Kf = KP
(∂KP/∂P)T = 0
But this does NOT mean that the amounts of various

gases at equilibrium do NOT change with pressure
Equilibrium Constant: Effect of Pressure
For the dissociation reaction A(g) ⇋ 2B(g), ∆ν > 0
n(1 − α) 2nα
xA = n(1 − α)/n(1 + α) = (1 − α)/(1 + α)

xB = 2nα/n(1 + α) = 2α/(1 + α)
PA = P (1 − α)/(1 + α) PB = P 2α/(1 + α)
KP = (PB)2 /PA KP = [P 2α/(1 + α)]2 / [P (1 − α)/(1 + α)]
KP is constant
KP = [4α2 /(1 − α2)]P
When P is small, α is large
α = √[KP /(KP + 4P)] When P is large, α is small
=> Le Chatelier’s Principle
Equilibrium Constant: Influence of Inert Gas
aA ⇋ bB
KP = (PB )b /(PA )a
= (xBP)b /(xAP)a Pi = xiP
KP = (xBP)b /(xAP)a KP = (xB)b /(xA)a (P)(b −a)
Kx = (xB)b /(xA)a KP = Kx (P)∆ν

If no moles of inert gas is introduced
xA = nA/(no+ nA+ nB) = nA/∑ni xB = nB/∑ni
For ∆ν = o, Eqm remains
KP = (nB/∑ni)b /(nA/∑ni )a (P)∆ν undisturbed;
For ∆ν > o, more products will
KP = (nB)b /(nA)a (P/ ∑ni )∆ν form;
For ∆ν < o, reaction will be
depressed
Le Chatelier’s Principle: (∂G/∂ξ)T, P = ΔrG = 0, at eqm.
Since (∂G/∂ξ)T, P is a We need only to determine the

sign of the derivatives
function of T, P, and ξ
(∂ξe/∂T)P and (∂ξe/∂P)T
d(∂G/∂ξ) = [∂(∂G/∂ξ)/∂T]dT + [∂(∂G/∂ξ)/∂P]dP + [∂(∂G/∂ξ)/∂ξ]dξ
Let [∂(∂G/∂ξ)/∂ξ] = G˝
d(∂G/∂ξ) = (∂ΔrG/∂T) dT + (∂ΔrG /∂P) dP + G˝dξ
d(∂G/∂ξ) = − ΔrS dT + ΔrVdP + G˝dξ
0 = − (ΔrH/T) (dT)e + ΔrV (dP)e + G˝d ξe
(∂ξe/∂T)P = ΔrH/(T G˝) (∂ξe/∂P)T = − ΔrV/G˝
At equilibrium, G is minimum, G˝ is positive
Equilibrium Constant: Effect of Catalyst
A catalyst is a substance that speeds up the rate of a
reaction without itself being used up
ΔrGo = ‒ RT lnKP
KP = exp (‒ ΔrGo/RT)
ΔrGo is a state function

and independent of
pathway
For a reaction mixture, that is not at equilibrium, a

catalyst will increase rates of both forward and reverse
reactions so that the equilibrium will reach sooner
A catalyst cannot shift the position of an equilibrium
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CHEMISTRY (CY11003)

Spring 2020 -2021

(∂G /∂ ξ)T, P = (μB ‒ μA )

(∂G /∂ ξ)T, P < 0, forward reaction => μA > μB

ni = nio + νi dξ or d(ni ‒ nio ) = νi dξ

(∂G /∂ ξ)T, P = ΔrG ΔrG = ∑νi μi

ΔrG > 0 reverse reaction is spontaneous (∂G /∂ ξ)T, P > 0

ΔrG = (∑νi μi )eq= 0 reaction is at equilibrium (∂G /∂ ξ)T, P,eq = 0

Gpure = ∑ni μi o(T, P)

ΔGmix = ∑ni (μi − μi o )

(∂Gpure /∂ξ)eq = − (∂ΔGmix /∂ξ)eq

ΔrG = ∑νi μi => ΔrG = bμB ‒ aμA

For ideal gases, μi = μio + RT ln Pi /Po where Po = 1 bar

μA = μAo + RT ln PA /Po μB = μBo + RT ln PB /Po

ΔrG = ΔrGo + RT ln[(PB /Po)b /(PA /Po)a ] ΔrG = ΔrGo + RT lnQ

ΔrGo = ∑νi μio ΔrGo = ‒ RT ln Kp Kp = [(PB /Po)b /(PA /Po)a ]eq

KP = ∏ xiνi P∆ν (Po)−∆ν KP = Kx (P/Po)∆ν

Pi = ci (co RT/ Po) KP = ∏ (ci)eνi (co RT/ Po)∆ν

KP = Kc (co RT/ Po)∆ν Kc = ∏ ciνi

Assuming ideal behavior, μA = μAo + RT ln (mA /mo)

ΔrGo = ‒ RT lnKm μB = μBo + RT ln (mB /mo)

Km = (mB /mo)b /(mA /mo)a For nonequilibrium reactions,

mo = 1 mol kg−1 = 1 m co = 1 mol L−1 = 1 M Q = ∏ miνi (mo)−∆ν

CaCO3 (s) ⇋ CaO (s) + CO2 (g)

K΄c = [CaO] [CO2] /[CaCO3]

K΄c × [CaCO3] /[CaO] = [CO2] Kc = [CO2]

KP = PCO2 / 1 bar Ka = aCaO aCO2 /aCaCO3

Ka = fCO2 / 1 bar aCaO = 1 and aCaCO3 = 1

ln(K2/K1) = ΔrHo/ R (T2 − T1)/ (T2T1)

ΔrGo = ΔrHo ‒ T ΔrSo

lnK = ‒ ΔrHo/RT +ΔrSo /R

ΔrHo(T) = ΔrHo(298) + ∫T ΔCp dT => ΔrHo(T) = ΔrHo(298) + ΔCp (T – 298)

ΔrSo(T) = ΔrSo(298) + ∫T (ΔCp/T) dT => ΔrSo(T) = ΔrSo(298) + ΔCp ln(T/298)

ΔrGo(T) = ΔrHo(T) – T ΔrSo(T) =>

ΔrGo(T) = ΔrHo(298) + ΔCp(T – 298) – T [ΔrSo(298) + ΔCp ln(T/298)]

ΔrGo(T) = ΔrHo(298) – T ΔrSo(298) + ΔCp (T – 298) – T ΔCp ln(T/298)

RTlnKT = RTlnK298 – ΔCp (T – 298) + T ΔCp ln(T/298)

lnKT – lnK298 = – ΔCp(T – 298)/RT + ΔCp ln(T/298)/R

KP is independent of P if the reaction involves ideal gases

KP does depend on P if the reaction involves real gases

For reactions involving ideal gases, Kf = KP

But this does NOT mean that the amounts of various

xA = n(1 − α)/n(1 + α) = (1 − α)/(1 + α)

Kx = (xB)b /(xA)a KP = Kx (P)∆ν

Since (∂G/∂ξ)T, P is a We need only to determine the

ΔrGo is a state function

For a reaction mixture, that is not at equilibrium, a

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